EP3692088A1 - Catalyseurs latents comportant des ligands chélateurs pour la polymérisation de dicyclopentadiène (dcpd) - Google Patents

Catalyseurs latents comportant des ligands chélateurs pour la polymérisation de dicyclopentadiène (dcpd)

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Publication number
EP3692088A1
EP3692088A1 EP18815588.1A EP18815588A EP3692088A1 EP 3692088 A1 EP3692088 A1 EP 3692088A1 EP 18815588 A EP18815588 A EP 18815588A EP 3692088 A1 EP3692088 A1 EP 3692088A1
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partially
branched
linear
arylene
group
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EP3692088C0 (fr
EP3692088B1 (fr
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Michael R. Buchmeiser
Iris Elser
Benjamin Richard Kordes
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Universitaet Stuttgart
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Universitaet Stuttgart
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B01J31/2278—Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
    • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/54—Metathesis reactions, e.g. olefin metathesis
    • B01J2231/543—Metathesis reactions, e.g. olefin metathesis alkene metathesis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/64—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B01J31/2269—Heterocyclic carbenes
    • B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
    • C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
    • C08G2261/3325—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from other polycyclic systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/418—Ring opening metathesis polymerisation [ROMP]

Definitions

  • the present invention relates to latent catalysts with chelating ligands based on molybdenum complexes for the polymerization of dicyclopentadiene (DCPD). Further aspects of the present invention relate to the use of these catalysts for the preparation of polymers such as polydicyclopentadienes and to processes for preparing corresponding polymers
  • Poly-DCPD is a polymeric active ingredient characterized by good chemical resistance, a high glass transition temperature of more than 130 ° C and a high corrosion resistance.
  • a further advantage of poly-DCPD is that this material can be painted or coated by oxidation of the surface after polymerization, without first having to apply a primer to the material or otherwise chemically pretreat the material.
  • a major advantage of poly-DCPD over conventional thermosets, such as polyesters and polyepoxides, is that the latter are relatively brittle, so additives are added, such as rubber or thermoplastic particles, to improve the toughness of these materials have to.
  • poly-DCPD has very good impact strengths and toughness even without additional additives, especially a favorable one
  • Poly-DCPD make a very high-performance thermosets. More recently, poly-DCPD has been used to manufacture large workpieces, such as body parts for tractors and trucks, or to coat industrial electrolysis cells.
  • ring-opening metathesis polymerization converted to poly-DCPD, for example, by the reaction injection molding (reaction injection molding).
  • reaction injection molding a reaction mixture of two components, of which the essential portion consists of endo-DCPD, mixed in an antechamber and then quickly transferred to the mold to completely cure there under heating.
  • a problem with the currently used methods is an unfavorably high reactivity of the catalyst which, in combination with the high reactivity of the DCPD monomer, renders the polymerization difficult to control.
  • a very narrow time window must be observed during the polymerization, so that it is not always possible to produce a uniform mixture and to distribute it evenly, in particular in the case of thin shaped bodies, in the mold.
  • Metton ® Poly-DCPD are tungsten (IV) chloride and tungsten (IV) with nonylphenol oxytetrachlorid part of component 1, while ethylaluminum chloride is used as a cocatalyst of the second component.
  • ruthenium-based catalysts have been proposed for the preparation of poly-DCPD, which can be selectively activated.
  • M. R. Buchmeiser et al. (Chemistry - A European Journal, 2010, 16, 12928-12934) proposed a catalyst which is only active by activation with UV light in the metathesis of DCPD.
  • the light activation allows a targeted initiation of the polymerization, but it is particularly suitable for the modification and functionalization of surfaces, since here an activation with light is easily possible if thin coating to be produced.
  • light-activated catalysts are less suitable.
  • Verpoort et al. describe in J. of Polym. Be. Part A: Polymer Chemistry, 2010, 48, p. 302-310 ruthenium catalysts of the formula shown below, which are inactive to DCPD at room temperature but can be activated by the addition of HCl as cocatalyst.
  • reaction mixture hardens relatively quickly after mixing the components, so that a rapid processing with the associated error sources is required.
  • a strategy for preparing a thermal latent catalyst in the literature has been to introduce a chelating alkylidene ligand into Grubbs first and second generation catalysts, the chelating catalyst being a Catalyst
  • Metal center loses the inhibitory effect after the first metathesis cycle, which allows a delay of the initiation rate at room temperature.
  • DCPD proposes a simple process management based on a one-component system containing all components, ie catalyst and Monomer (eg DCPD) is allowed.
  • ie catalyst and Monomer eg DCPD
  • One-component system should also have a sufficient shelf life ("pot life") within which there is no appreciable polymerization and thus no change in viscosity. Nevertheless, when activated, the catalyst should have a sufficiently high activity to allow a cured polymer to be obtained in a short time.
  • the aim of the present invention was therefore also to propose catalysts for the polymerization of DCPD, which are characterized by a good stability to atmospheric oxygen
  • Catalysts based on molybdenum or tungsten appear to be particularly suitable, is currently known for the ROMP no suitable thermally activatable catalyst.
  • a first aspect of the present invention relates to a catalyst according to the general formula I or II
  • a 1 is NR 2
  • a 2 is CR 2 R 2 ' or NR 2
  • a 3 is N
  • C stands for a carbene carbon atom
  • the ring B is an unsubstituted or a mono- or polysubstituted 5- to 7-membered ring, in addition to A 1 , A 2 and A 3 at least one other
  • the ring D is an unsubstituted or a mono- or polysubstituted 5- to 7-membered, preferably a 6-membered, Ring which, in addition to N, may contain one or more further heteroatoms in the form of nitrogen, phosphorus, oxygen and or sulfur, and is preferably aromatic,
  • R 2 , R 2 ' and R 3 independently of one another, denote H, a linear, partially cyclic or branched C 1 -C 6 -alkyl-, a linear, partially cyclic or branched C 2 -C 18 -alkenyl, a C 3 -C 12 -cycloalkyl- , a linear, partially cyclic or branched Ce-Cioo-polyoxaalkyl, a C 5 -C 4 -aryl or heteroaryl radical, a C 5 -C 14 -aryloxy, a linear, partially cyclic or branched C 1 -C 6 -perfluoroalkyl radical, a linear, partially cyclic or branched C 1 -C 6 -perchloroalkyl, a linear, partially cyclic or branched partially fluorinated C 1 -C 6 -alkyl-,
  • R 2 may be the same or different, wherein the C5-C14 aryl or heteroaryl residues and Cs-Ci 4 -Aryloxyreste with one or more linear, partially cyclic or branched C 1 -C 6 -alkyl radicals, may be substituted,
  • X 1 or X 2 in formulas I to II are identical or different and from the group comprising Ci-Cie carboxylates, Ci-Cis alkoxides, fluorinated Ci-Cie alkoxides, Ci-Cie mono- or polyhalogenated carboxylates, a - or polysubstituted Ce-cis mono-, bi- or terphenolates, trifluoromethanesulfonate, trifluoroacetate, chloride, bromide or iodide are selected, wherein the substituents on the mono-, bi- or terphenolates in addition to halogen may have the same meaning as R 2 ,
  • Y is an N-adamantyl, an N-tert-butyl or a C 6 -C 4 -N-aryl radical, in particular a Ce-Cio-N-aryl radical, where the aryl radical is mono- or polysubstituted with halogen, a linear or branched Ci-Cie alkyl, a linear or branched Ci-Cis alkyloxy and / or an unsubstituted or substituted phenyl radical may be substituted, whose substituents have the same meaning as R 2 , Z is a linear, partially cyclic or branched Ci-Cio-alkylene, a linear, partially cyclic or branched Ci-Cio-Alkylenoxy-, a linear, teilcyclische or branched Ci-Cio-Alkylenenthio-, a linear, teilcyclische or branched Ci-Cio alkylene NR 2 -, a C 6 -C
  • aliphatic or aromatic radical in particular a linear or branched Ci-Cie alkyl group, or an unsubstituted or mono- or polysubstituted C 6 -C 4 -aryl group, wherein the substituents have the meanings given for R 2 .
  • the invention relates to the use of these catalysts for the preparation of polymers by ring-opening metathesis polymerization (ROMP), a
  • Embodiments of the application theory of the invention and the claims 13 to 15 represent preferred embodiments of the method of the invention.
  • the above catalysts are "latent" in terms of ring-opening metathesis polymerization, i. that they do not initiate metathesis polymerization at ambient temperature (25 ° C) without external stimulation.
  • Stimulation of the catalysts is usually carried out by heating the catalyst in mixture with the monomer / monomers to be polymerized.
  • Particularly suitable are methyl, ethyl and propyl groups.
  • the linear, partially cyclic or branched C 2 -Cis-alkenyl group is
  • C 2 -Cio-alkenyl group suitably in the form of a C 2 -Cio-alkenyl group, in particular in the form of a C 2 -C 7 -alkenyl group and preferably in the form of butenyl or hexenyl before.
  • C 3 -C 2 cycloalkyl group it is preferred if this in the form of a C3-C 6 - cycloalkyl group present.
  • Suitable groups in this context are cyclopentyl and cyclohexyl.
  • R 2 or R 2 ' is a linear, partially cyclic or branched Ce-Cioo-polyoxaalkyl radical
  • Suitable radicals are, for. For example, methyloxyethyl or methyloxyethyloxy.
  • the substituted or unsubstituted C 5 -C 4 -aryl or -Heteroarylrest is preferably in the form of a C 6 -C 4 -aryl or -Heteroarylrests, in particular a Ce-Cio-aryl or -Heteroaryl residue before.
  • phenyl, naphthyl or ferrocenyl have been found to be particularly suitable.
  • C 5 -C 4 -aryloxy radicals C 6 -C 4 -aryloxy radicals and in particular Ce-Cio-aryloxy radicals are preferred.
  • Particularly suitable unsubstituted aryloxy radicals are phenyloxy or naphthyloxy.
  • the linear, partially cyclic or branched Ci-Cis-perfluorinated alkyl radical is in particular in the form of a Ci-Cio-perfluorinated alkyl radical, preferably in the form a C 1 -C 7 perfluorinated alkyl radical, and more preferably in the form of a C 1 -C 4 perfluoroalkyl radical, with trifluoromethyl as the remainder being most preferred.
  • the linear, partially cyclic or branched Ci-Cis-perchlorinated alkyl radical in particular in the form of a Ci-Cio-perchlorinated alkyl radical, preferably in the form of a Ci-C 7 -perchlor faced alkyl radical and particularly preferably in the form of a Ci C 4 perchloroalkyl radical, with trichloromethyl being the most preferred radical.
  • the linear, partially cyclic or branched partially fluorinated C 1 -C 6 -alkyl radical is preferably present as a partially fluorinated C 1 -C 10 -alkyl radical, and in particular as a partially fluorinated C 1 -C 7 -alkyl radical.
  • An example of such a radical is trifluoroethyl.
  • the linear, partially cyclic or branched partially chlorinated C 1 -C 6 -alkyl radical is preferably present as a partially chlorinated C 1 -C 10 -alkyl radical and in particular as a partially chlorinated C 1 -C 7 -alkyl radical.
  • An example of such a radical is trichloroethyl.
  • the perfluorinated Cs-C 4 aryl moiety is 4-aryl radical, preferably a perfluorinated Ce-Cio-aryl radical, and particularly preferably in the form of a Pentafluorophenylrests particular as perfluorinated Ce-Ci.
  • the partially fluorinated Cs-C is a 4-aryl radical, in particular as partially fluorinated Ce- Ci 4-aryl radical, preferably a partially fluorinated Ce-Cio-aryl radical, and particularly preferably in the form of Fluorophenyl before.
  • the perchlorinated Cs-C 4 aryl radical is, in particular as a perchlorinated C 6 -C 4 - aryl radical, preferably as a perchlorinated Ce-Cio-aryl radical, and particularly preferably in the form of a Pentachlorophenylrests before.
  • Partly chlorinated Cs-C 4 aryl radical in particular as teilchlorierter Ce- Ci 4-aryl radical, preferably as teilchlorierter Ce-Cio-aryl radical, and particularly preferably in the form of chlorophenyl before.
  • Ci-C7-alkyl radicals be substituted.
  • R 2 and R 2 ' may be the same or different.
  • the substituent R 2 if it is bonded directly to one of the substituents A 1 or A 2 , that it is a substituent other than hydrogen.
  • R 2 and R 2 ' together form a linear or branched C 1 -C 6 -alkylene group, this is preferably present as C 1 -C 7 -alkylene group and particularly preferably in the form of a butylene or pentylene group.
  • R 3 is preferably a per-, partly-, or unhalogenated alkyl radical, unhalogenated C 1 -C 6 -alkyl radicals, in particular unhalogenated C 1 -C 6 -alkyl radicals, being more preferred. Most preferably, R 3 is a methyl radical.
  • a 1 is NR 2
  • a 2 is NR 2 or CR 2 R 2 ' and preferably NR 2 .
  • the ring B is a heterocyclic 5- to 7-membered ring at least one adjacent to the carbenoid carbon (i.e., the carbon atom which is in the form of a carbene)
  • Nitrogen atom and further comprises either another nitrogen atom or quaternary carbon atom.
  • the heterocyclic 5- to 7-membered ring may have at least one further heteroatom, which may be a nitrogen, phosphorus, oxygen or sulfur atom.
  • the nitrogen atoms or phosphorus atoms are in this case incorporated into a double bond or have a substituent R 2 which is not present in the form of hydrogen, so that the nitrogen or phosphorus atoms in the ring B are tertiary amines or phosphines.
  • heterocyclic ring B may be substituted, for example, with phenyl or with another preferably aromatic ring form a bicyclic or polycyclic system.
  • the ring B may be at a benzannelated, naphthannated, phenanthrene or anthraquinone fused 5- to 7-membered ring.
  • ring B is one selected from the group comprising imidazol-2-ylidene,
  • the ring is mono- or polysubstituted and has one or more substituents which are selected from linear, partially cyclic or branched C 1 -C 6 -alkyl, in particular C 1 -C 7 -alkyl radicals and C C 5 -C 4 -aryl or heteroaryl radicals and C 5 -C 4 -aryloxy radicals which are substituted by one or more linear, partially cyclic or branched C 1 -C 6 -alkyl radicals, in particular C 1 -C 7 -alkyl radicals.
  • Particularly preferred rings B in the context of the present invention are a 1-mesitylene-3-picolylimidazol-2-ylidene radical and a 1,3-bismesitylenimidazolimidazol-2-ylidene radical.
  • the ring D is a heterocyclic 5- to 7-membered ring, which in addition to N may contain one or more heteroatoms in the form of nitrogen, phosphorus, oxygen or sulfur. If the ring D contains further heteroatoms then nitrogen and oxygen are preferred, nitrogen is usually preferred. However, it is also possible, and may be considered preferable, if the ring D contains no further heteroatoms in addition to the N atom coordinating the molybdenum.
  • the ring D may be aliphatic or aromatic, with aromatic being preferred. Alternatively or additionally, it is preferred that the ring D is a 5- to 6-membered ring, more preferably a 6-membered ring. Most preferably, ring D is a pyridyl ring.
  • the metal in the catalyst is molybdenum.
  • Ci-Cs-carboxylate is particularly suitable carboxylates.
  • Particularly suitable carboxylates are acetate, propionate and benzoate.
  • At least one of the two substituents X 1 and X 2 is present in the form of a C 1 -C 6 -alkoxide, it is preferred if this is a C 1 -C 5 -alkoxide.
  • Particularly suitable alkoxides are 2-propoxide and tert-butoxide.
  • At least one of the two substituents X 1 and X 2 is present in the form of a fluorinated C 1 -C 6 -alkoxide, it is preferred if this is a fluorinated C 1 -C 5 -alkoxide.
  • Particularly suitable fluorinated alkoxides are the hexafluoro-2-propoxide and a hexafluoro-tert-butoxide.
  • Ci-Cis-carboxylate If at least one of the two substituents X 1 and X 2 in the form of a mono- or polyhalogenated Ci-Cis-carboxylate, it is preferred if it is a mono- or polyhalogenated Ci-Cs-carboxylate. As particularly suitable mono- or polyhalogenated Ci-Cis carboxylates are
  • Preferred mono-, mono- or polysubstituted mono-, bi- or terphenolates are the 2,6-diphenylphenolate, 2 ', 2 ", 6', 6" -tetrakis (2-propyl) -2,6-diphenylphenolate and the 2 ', 2', 6 ', 6 "-tetramethyl-2,6-diphenylphenolat.
  • Substituents such as fluorinated and non-fluorinated C 1 -C 6 -alkoxides, in particular in the form of C 1 -C 4 -alkoxides, can be used for the substituents X 1 and X 2 .
  • Particularly suitable alkoxides are ethanolate, 2-propanolate, tert-butoxide, hexafluoro-2-propoxide or hexafluoro-tert-butoxide.
  • X 1 or X 2 in formulas I to II are selected from C 1 -C 6 -alkoxides, in particular from C 1 -C 7 -alkoxides, and trifluoromethanesulfonate.
  • the C 6 -C 4 -N-aryl radical is preferably present in the form of a Ce-Cio-N-aryl radical, where the aryl radical is mono- or polysubstituted by halogen, C 1 -C 6 -alkyl radicals, in particular C 1 -C 4 -N-aryl radicals -Cs-alkyl radicals, Ci-Cis-alkyloxy radicals, in particular Ci-Cs Alkyloxy radicals, with methoxy or 2-propoxy groups being particularly preferred, or an unsubstituted or substituted phenyl radical whose
  • Substituents may have the same meaning as indicated for R 2 , may be substituted.
  • substituents Y are, in particular, 2,6- and 3,5-disubstituted N-aryl radicals, preferably in the form of N-phenyl radicals, in which the substituents are preferably alkyl radicals, such as tert-butyl, iso-propyl or methyl, or as halogens, such as chlorine, fluorine or bromine or
  • substituents Y are N-alkyl radicals in which the carbon atom is in direct proximity to the
  • Nitrogen is a quaternary carbon atom.
  • N-alkyl radicals are the N-tert-butyl or the N-adamantyl radical.
  • Particularly preferred substituents Y are in the context of the present invention, the N-2,6-dimethylphenyl, the N-
  • the linear, partially cyclic or branched C 1 -C 10 -alkyleneoxy group is preferably a C 1 -C 3 -alkyleneoxy group and in particular an ethyleneoxy group
  • the linear, partially cyclic or branched C 1 -C 10 -alkylenethio group is preferably a C 1 -C 3 -alkylenethio group and in particular an ethylene thio group
  • the linear, partially cyclic or branched C 1 -C 10 -alkylene NR 2 group is preferably a C 1 -C 3 -alkylene-NR 2 group and in particular an ethylene-NR 2 group
  • the Ce-Cio-arylene group is preferably a phenylene group and
  • the C 6 -C 4 -aryleneoxy group is preferably a Ce-Cio-aryleneoxy group, and in particular a 2-phenyleneoxy group;
  • the perfluorinated C 6 -C 4 -aryleneoxy group is preferably a perfluorinated C 6 -C 10 -aryleneoxy group and in particular a tetrafluorophenyl-2-enoxy group;
  • the partially fluorinated C 6 -C 4 -aryleneoxy group is preferably a partially fluorinated C 6 -C 10 -aryleneoxy group and in particular a fluorophenyl-2-enoxy group;
  • the perchlorinated C 6 -C 4 -aryleneoxy group is preferably a perchlorinated C 1 -C 10 -aryleneoxy group and in particular a te
  • Carbon atom in R 1 which is in direct proximity to the metal alkylidene, a quaternary carbon atom having no hydrogen substituent.
  • Suitable substituents of this quaternary carbon atom include, inter alia, the radicals listed for the substituents R 2 . Based on these specifications, a suitable substituent R 1 can be expertly selected.
  • R 1 in the formulas I and II is tert-butyl, an unsubstituted or substituted phenyl, such as 2- (2-propoxy) phen-1-yl, 2-methoxyphen-1-yl, 2,4,5-trimethoxyphenyl, or ferrocenyl or CMe 2 Ph, wherein the substituents on the phenyl may have the same meaning for as R 2 given, but in particular 2- (2-propoxy) - or 2-methoxy substituents may be ,
  • 2- (2-propoxy) - or 2-methoxy substituents may be advantageous
  • C 1 -C 6 -alkyl group is a C 1 -C 10 -alkyl group and C 6 -C 4 -aryl is a C -C -aryl aryl group.
  • R 1 tert-butyl, an unsubstituted or substituted phenyl, ferrocenyl or CMe 2 Ph can be given.
  • the substituent Z may contain further substituents, but it may also be unsubstituted.
  • the catalyst is a catalyst according to the formula G:
  • the catalyst is a complex according to the formula II, it is particularly preferred if Z is a substituent with an atom, preferably a carbon atom, between A 3 and the ring D in the formula II, more preferred it, when the substituent is a methylene.
  • the substituent Z may contain further substituents, but it may also, as in a
  • the catalyst is a catalyst according to the formula IG:
  • a further aspect of the present invention deals with the use of the catalyst according to the invention for the preparation of polymers by a ring-opening metathesis polymerization (ROMP).
  • the polymers thus prepared can be used, for example, as matrix polymers for fibrous matrix composites, as compatibilizers or as base polymers for fibers.
  • Preferred monomers for preparing corresponding polymers include cyclic olefins, such as cyclobutene, cyclopentene, Dicyclopentadiene, cyclohexene, cycloheptene, cis-cyclooctene, cyclooctatetraene, [2.3.0] bicycloheptene and norbornene, and derivatives thereof.
  • a particularly suitable monomer in the context of the present invention is dicyclopentadiene.
  • Monomers for the ROMP characterized by their latency, i. that they are quasi non-reactive with the monomers at ambient temperature (25 ° C), while heating the reaction mixture allows a controlled polymerization.
  • dicyclopentadiene represents a particularly reactive monomer in the context of ROMP and ruthenium-based catalysts generally do not give any storage-stable mixtures
  • a particularly preferred aspect of the use of the invention relates to the preparation of
  • Catalysts according to the invention found favorable latency with particular advantage for carrying.
  • a preferred use relates to the use of
  • a further aspect of the present invention relates, as mentioned above, to a process for the preparation of polymers by ring-opening
  • Metathesis polymerization comprising the following steps:
  • reaction mixture is heated to a temperature of at least 60 ° C, more preferably at least 80 ° C, and most preferably at least 100 ° C.
  • the temperature to which the reaction mixture is heated should not be too high so that unwanted decomposition of the catalyst and / or the polymer can not occur.
  • a temperature of about 250 ° C and preferably at most 200 ° C can be specified in this context.
  • the amount of catalyst involved in the process is not critical. On the one hand, however, the amount should be high enough for the polymerization to proceed quickly enough after activation for the industrial application. On the other hand, the amount of catalyst should be as low as possible from a cost point of view.
  • a suitable amount of catalyst a range of 0.0001 to 5 mol% (based on the molar amount of the monomer (s) used), especially 0.001 to 1 mol%, and particularly preferably 0.05 to 0.5 mol% can be given.
  • Reaction mixture in a preferred aspect of the above-described process before heating in (ii) applied as a coating on a substrate there are no relevant limitations, i. it may be a metal, a plastic or another substrate, wherein metal and plastic substrates are to be specified as preferred.
  • the method according to the invention can be advantageously designed by being carried out as a reaction injection molding method, transfer molding method or resin injection method.
  • the corresponding processes and their implementation are readily familiar to the person skilled in the art.
  • a final aspect of the present invention finally concerns a
  • Polydicyclopentadiene which is prepared by the method described above. As shown in the following examples, the polycyclopentadienes prepared by such a process are characterized by a Compared to classical Grubbs catalysts
  • Polycyclopentadienes are less swellable, which in turn suggests a higher degree of crosslinking. This in turn can be
  • the polycyclopentadiene has a swelling capacity determined as described in the examples section of 100% or less, more preferably 50% or less, even more preferably 30% or less, even more preferably 10% or less and most preferably 2% or less.
  • l-Mesityl-3-picolylimidazolium bromide (429 mg, 1.2 mmol) was dissolved in benzene and a solution of KHMDS (239 mg, 1.2 mmol) in benzene was added. After one hour, the brown-red suspension was filtered through Celite. The filtrate was added slowly to a solution of Mo (N-2,6-Me 2 -C 6 H 3 ) (CHC Me 2 Ph) (OTf) 2 DME (880 mg, 1.20 mmol) in benzene. After a few minutes, the formation of a yellow precipitate was observed.
  • the respective catalyst (1 eq., Ca. 4-7 mg) was suspended in 1,2,4-trichlorobenzene (10 eq, ca. 3-7 pL) and DCPD (100 eq.) was added. The mixture was stirred for five minutes at room temperature and a sample of the DSC measurements were taken. The DSC crucibles were pressed in a protective gas box and the sample was subjected to a temperature scan DSC measurement. T onset, T s can was defined as the temperature at which the exothermic reaction began. T exo, max was defined as the minimum of the DSC curve. In addition, all samples were subjected to a second temperature scan DSC measurement to ensure complete cure.
  • Heating program TScan 0 ° C for 1 minute
  • Example 7 Determination of T on set, isothermai for Catalysts 3 and 4
  • the catalyst (1 eq., Ca. 4-7 mg) was dissolved in 1,2,4-trichlorobenzene (10 eq, ca. 3-7 pL). and DCPD (100 eq.) was added. The mixture was stirred for five minutes at room temperature and a sample was taken for DSC measurements. The DSC crucibles were pressed in a protective gas box and the samples for the isothermal DSC measurements were taken. The samples were subjected to isothermal DSC measurements and subsequent temperature-scan measurements to ensure complete cure.
  • T on set, isothermai was defined as the maximum temperature at which a sample could be heated for thirty minutes without polymerizing. For this purpose, the determined reaction enthalpies from the temperature scan of the thermally pretreated sample were compared with the untreated sample.
  • Heating program for isothermal measurements Specified temperature for thirty
  • Example 7 Determination of the Latency of Catalysts 1 to 4
  • the catalyst (1 eq., About 4-7 mg) was suspended in 1,2,4-trichlorobenzene (10 eq., About 3-7 ⁇ L) and DCPD ( 100 eq.) was added.
  • the mixture was stirred for five minutes at room temperature and a sample was taken for DSC measurements.
  • the DSC crucibles were pressed in a protective gas box. The mixture was stirred at room temperature in the protective gas box and after the specified time another sample was taken.
  • a catalyst was defined as latent when the reaction enthalpy of the aged sample corresponded to that of the reference.
  • Heating program TScan 0 ° C for 1 minute
  • n.b not determined.
  • Example 8 Determination of Swelling Capacity of Poly-DCPD Produced by Catalysts 1-4
  • the degree of cross-linking is inversely proportional to the degree of swelling
  • the degree of swelling Q was determined.
  • the corresponding polyreaction was carried out in a glass cylinder (12 mm diameter).
  • the catalyst (1 eq, ca. 5-7 mg) was suspended in 1,2,4-trichlorobenzene (10 eq, ca. 5-10 pL) and DCPD (250 eq.) was added.
  • the mixture was heated at the temperature indicated in Table 4 for 30 to 90 minutes.
  • the resulting polymer was vacuum dried for twelve hours. The mass was determined (m 0 ).
  • toluene (3 mL) was added. After two days, the toluene was decanted off and the mass of the swollen polymer (m s ) was determined.
  • the results of these determinations are given for the catalysts 1 to 4 in the following Table 4.

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne des catalyseurs selon les formules I et II pour la polymérisation par métathèse d'ouverture de cycle (ROMP), A1 étant NR2, A2 étant CR2R2' ou NR2, A3 étant N et C étant un atome de carbone-carbène. Les catalyseurs sont particulièrement destinés à la polymérisation par métathèse d'ouverture de cycle de dicyclopentadiène, du fait qu'ils se caractérisent par une stabilité et une latence avantageuses de telle manière qu'ils ne réagissent avec les monomères dicyclopentadiène qu'à température accrue. D'autres aspects de la présente invention concernent l'utilisation de catalyseurs correspondants pour la production de polymères par polymérisation par métathèse d'ouverture de cycle ainsi que des procédés de production de polymères correspondants dont la polymérisation est initiée par chauffage du mélange réactionnel.
EP18815588.1A 2017-12-19 2018-11-30 Catalyseurs latents comportant des ligands chélateurs pour la polymérisation de dicyclopentadiène (dcpd) Active EP3692088B1 (fr)

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DE102017130504.1A DE102017130504A1 (de) 2017-12-19 2017-12-19 Latente Katalysatoren mit Chelatliganden zur Polymerisation von Dicyclopentadien (DCPD)
PCT/EP2018/083208 WO2019120950A1 (fr) 2017-12-19 2018-11-30 Catalyseurs latents comportant des ligands chélateurs pour la polymérisation de dicyclopentadiène (dcpd)

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